Inorganic fullerene-like particles and inorganic tubular-like particles in fluids and lubricants and applications to subterranean drilling

ABSTRACT

A drilling fluid including a drilling fluid medium selected from the group consisting of water, air and water, air and foaming agent, a water based mud, an oil based mud, a synthetic based fluid, and a composition thereof. The drilling fluid also includes at least one intercalation compound of a metal chalcogenide having molecular formula MX2, where M is a metallic element such as tungsten (W), and X is a chalcogen element such as sulfur (S), wherein the intercalation compound has a fullerene-like hollow structure or tubular-like structure.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/766,431 filed Feb. 19, 2013, titled “INORGANIC FULLERENE-LIKEPARTICLES AND INORGANIC TUBULAR-LIKE PARTICLES IN FLUIDS AND LUBRICANTSAND APPLICATIONS TO SUBTERRANEAN DRILLING”, which is incorporated hereinin its entirety by reference.

FIELD OF THE INVENTION

The present disclosure relates to inorganic particles having afullerene-like and tubular-like geometry in a fluid lubricant. In someembodiments, the inorganic particles with the fullerene-like andtubular-like geometry are employed in a drilling fluid.

BACKGROUND

Oils and lubricants are used for a variety of applications, includingproviding lubrication for engines and motors to extend lifetime andprevent failure. Oils that are used as lubricants provide lubricationbetween two moving surfaces, such as for example, bearings and othermetal surfaces.

Drilling fluids (muds) are normally used in drilling oil and gas wells.These fluids are used to maintain pressure, cool drill bits, and lift,cuttings from the holes as the well is being drilled. Drilling fluidsvary greatly in composition depending upon specific requirements of thewell being drilled, as well as geological considerations.

SUMMARY

In one embodiment of the present disclosure, a lubricant is provided. Inone embodiment, the lubricant comprises a fluid medium and at least oneintercalation compound of a metal chalcogenide having molecular formulaMX₂, where M is a metallic element selected from the group consisting oftitanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe),cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr),niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium(Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum(Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum(Pt), gold (Au), mercury (Hg) and combinations thereof, and X is achalcogen element selected from the group consisting of sulfur (S),selenium (Se), tellurium (Te), oxygen (O) and combinations thereof. Theintercalation compound has at least one of a fullerene-like structure ortubular-like structure. The intercalation compound is present in thelubricant in an amount of greater than 0.1 wt %. The lubricant furtherincludes a functionalizing agent. The functionalizing agent providesthat the intercalation compound is kept in suspension within the fluidmedium.

In another embodiment, a drilling fluid is provided. The drilling fluidincludes a drilling fluid medium selected from the group consisting ofwater, air, and water, air and foaming agent, a water based mud, an oilbased mud, a synthetic based fluid, and a combination thereof. Thedrilling fluid further comprises at least one intercalation compound ofa commercial chalcogenide having molecular formula MX₂, where M is ametallic element selected from the group consisting of titanium (Ti),vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co),nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb),molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh),palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta),tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt),gold (Au), mercury (Hg) and combinations thereof, and X is a chalcogenelement selected from the group consisting of sulfur (S), selenium (Se),tellurium (Te), oxygen (O) and combinations thereof. The intercalationcompound has a fullerene-like structure or tubular-like structure. Theintercalation compound is present in the drilling fluid an amount ofgreater than 0.1 wt %.

In another aspect, a subterranean drilling method is provided thatincludes providing a drilling member, applying the drilling member to asurface to form a subterranean wellbore, and lubricating at least one ofthe subterranean wellbore and the drilling member with a drilling fluidincluding at least one intercalation compound of a metal chalcogenidehaving molecular formula MX₂, where M is a metallic element selectedfrom the group consisting of titanium (Ti), vanadium (V), chromium (Cr),manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc(Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc),ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd),hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os),iridium (Ir), platinum (Pt), gold (Au), mercury (Hg) and combinationsthereof, and X is a chalcogen element selected from the group consistingof sulfur (S), selenium (Se), tellurium (Te), oxygen (O) andcombinations thereof. The intercalation compound has a fullerene-likestructure or tubular-like structure. The intercalation compound ispresent in the drilling fluid in an amount of greater than 0.1 wt % byweight.

BRIEF DESCRIPTION OF DRAWINGS

The following detailed description, given by way of example and notintended to limit the disclosure solely thereto, will best beappreciated in conjunction with the accompanying drawings, wherein likereference numerals denote like elements and parts, in which:

FIG. 1 is a transmission electron microscope (TEM) image of anintercalation compound of a metal chalcogenide having molecular formulaMX₂ having a fullerene-like geometry, in accordance with one embodimentof the present disclosure.

FIG. 2 is a transmission electron microscope (TEM) image of anintercalation compound of a metal chalcogenide having molecular formula.MX₂ having a tube-like geometry, in accordance with one embodiment ofthe present disclosure.

FIGS. 3 and 4 are pictorial views depicting an intercalation compoundthat is in simultaneous contact with two surfaces being lubricated by arolling action of the intercalation compound, in accordance with oneembodiment of the present disclosure.

FIG. 5 is a pictorial view depicting a layer of the intercalationcompound adhering to a surface that is being lubricated by theintercalation compound, in accordance with one embodiment of the presentdisclosure.

FIG. 6 is a pictorial view of a drilling operation using the drillingfluid including the intercalation compound of a metal chalcogenidehaving molecular formula MX₂, which has a fullerene-like and/ortube-like geometry, in accordance with one embodiment of the presentdisclosure.

FIG. 7 is a plot of data from a pin on disc test for drilling fluidincluding the intercalation compound of a metal chalcogenide havingmolecular formula MX₂, which has a fullerene-like and/or tube-likegeometry in comparison to a drilling fluid without the intercalationcompound, in accordance with one embodiment of the present disclosure.

FIG. 8 depicts profilometry curves for the ball from the pin on disctest that provided the data in FIG. 7.

FIGS. 9A, 9B and 9C are optical microscope images of the ball from thepin on disc test that provided the data in FIG. 7.

FIG. 10 is a plot of engine wear (measured by presence of iron (Fe) inoil (ppm) as a function of engine run time for a sample of 30 SAE oilincluding at least one intercalation compound of a metal chalcogenidehaving molecular formula MX₂ in comparison with a comparative sample of30 SAE oil without the intercalation compound.

DETAILED DESCRIPTION

Detailed embodiments of the present disclosure are described herein;however, it is to be understood that the disclosed embodiments aremerely illustrative of the compositions, structures and methods of thedisclosure that may be embodied in various forms. In addition, each ofthe examples given in connection with the various embodiments areintended to be illustrative, and not restrictive. Further, the figuresare not necessarily to scale, some features may be exaggerated to showdetails of particular components. Therefore, specific structural andfunctional details disclosed herein are not to be interpreted aslimiting, but merely as a representative basis for teaching one skilledin the art to variously employ the compositions, structures and methodsdisclosed herein. References in the specification to “one embodiment”,“an embodiment”, “an example embodiment”, etc., indicate that theembodiment described may include a particular feature, structure, orcharacteristic, but every embodiment may not necessarily include theparticular feature, structure, or characteristic. Moreover, such phrasesare not necessarily referring to the same embodiment.

In one embodiment, a lubricant is provided that includes a fluid mediumand at least one intercalation compound of a metal chalcogenide havingmolecular formula MX₂ that is in suspension in the fluid medium, where Mis a metallic element selected from the group consisting of titanium(Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt(Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb),molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh),palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta),tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt),gold (Au), mercury (Hg) and combinations thereof, and X is a chalcogenelement selected from the group consisting of sulfur (S), selenium (Se),tellurium (Te), oxygen (O) and combinations thereof.

The fluid medium may be water based, oil based or can be an emulsion ofwater and oil. In one example, the fluid medium is an oil selected fromGroup I, II, III, IV and V, as designated by the American PetroleumInstitute (API). Group I base oils are classified as less than 90percent saturates, greater than 0.03 percent sulfur (S) with aviscosity-index range of 80 to 120. In some embodiments, the temperaturerange for these oils is from 32 degrees F. to 150 degrees F. Group Ibase oils can be manufactured by solvent extraction, solvent orcatalytic dewaxing, and hydro-finishing processes. Common Group I baseoil may include 150SN (solvent neutral), 500SN, and 150BS (brightstock).Group I base oils are typically mineral oils.

Group II base oils are defined as being more than 90 percent saturates,less than 0.03 percent sulfur and with a viscosity index of 80 to 120.Group II base oils can be often manufactured by hydrocracking. Since allthe hydrocarbon molecules of these oils are saturated, Group II baseoils have better antioxidation properties than Group I base oils. GroupII base oils are also typically mineral oils.

Group III base oils are defined as being greater than 90 percentsaturates, less than 0.03 percent sulfur and have a viscosity indexabove 120. These oils are refined even more than Group II base oils andgenerally are hydrocracked with a higher pressure and heat than GroupII. The processing for forming Group III base oils are typically longerthan the processing for Group II base oils, and are designed to achievea purer base oil. Although typically made from crude oil, Group III baseoils are sometimes described as synthesized hydrocarbons. Group III baseoils can be manufactured by processes, such as isohydromerization, andcan be manufactured from base oil or slax wax from dewaxing process.

Group IV base oils are polyalphaolefins (PAOs). These synthetic baseoils are made through a process called synthesizing. More specifically,in some embodiments, the process may begin with oligomerisation of alphaolefins and a catalyst. Oligomerization is followed by distillation. Theoligomerization and distillation steps may include steam crackinghydrocarbons to produce ultra high-purity ethylene, ethyleneoligomerization to develop 1-decene and 1-dodecene, and decene ordodecene oligomerization to form a mixture of dimers, trimers, tetramersand higher oligomers. Distillation is followed by hydrogenationincluding hydrogen and a catalyst. Group IV base oils such aspolyalphaolefins (PAOs) are suitable for a broader temperature rangethat Group I, II and III base oils, and are applicable for use inextreme cold conditions and high heat applications. Group IV base oilstypically have a viscosity index of at least 140.

Group V base oils are classified as all other base oils, includingsilicone, phosphate ester, polyalkylene glycol (PAG), polyolester,biolubes, etc. These base oils are at times mixed with other basestocks, such as the aforementioned Group I, II, III and IV base oils. Anexample would be polyalphaolefin (PAO) that is mixed with a polyolester.Esters are common Group V base oils used in different lubricantformulations to improve the properties of the existing base oil. In someembodiments, ester oils can take more abuse at higher temperatures andwill provide superior detergency compared to a polyalphaolefin (PAO)synthetic base oil, which in turn increases the hours of use. Examplesof synthetic oils include olefins, isomerized olefins, synthetic esters,phosphate esters, silicate esters, polyalkylene glycols, etc.

In another embodiment, the fluid component, i.e., fluid medium, of thelubricant can be a biolubricant. Biolubricants can primarily betriglyceride esters derived from plants and animals. Examples ofbiolubricants that are suitable for the fluid component that is mixedwith the intercalation compound of the metal chalcogenide having themolecular formula MX₂ include lanolin, whale oil, canola oil, castoroil, palm oil, sunflower seed oil, rapeseed oil and tall oil.

In one example, the fluid medium is a water based fluid. The water basedfluid may be a fluid or gel that is made from a base of water andtypically a cellulose or glycerin solution. A water based fluid may beused on its own or in combination with other materials described hereinto provide the fluid medium of the lubricant. It is noted that the abovecompositions provided for the fluid medium of the lubricants disclosedherein are provided for illustrative purposes only, and are not intendedto limit the present disclosure. Other compositions and fluids have alsobeen contemplated for use with the at least one intercalation compoundof the metal chalcogenide having molecular formula MX₂.

The term “intercalation compound” denotes a compound that can beinserted between elements or layers. The intercalation compoundtypically has a fullerene-like or tube-like geometry. As used herein,the term “inorganic fullerene-like” denotes a sphere like geometry. Thecore of the fullerene-like geometry may be hollow, solid, amorphous, ora combination of hollow, solid and amorphous portions. A fullerene-likegeometry may also be referred to as having a cage geometry. Morespecifically, in some embodiments, an intercalation compound having aninorganic fullerene like geometry may be a cage geometry that is hollowor solid at its core and layered at its periphery. For example, theintercalation compound having the inorganic fullerene like geometry maybe a single layer or double layered structure. The intercalationcompound is not limited on only single layer or double layeredstructures, as the intercalation compound may have any number of layers.These structures are also referred to in the art as being “nested layerstructures”. The inorganic fullerene like geometry of the nanoparticlesmay be spherical or near spherical, or may have a polyhedral geometry,with or without a hollow core.

One example of an intercalation compound having an inorganicfullerene-like geometry is depicted in FIG. 1. FIG. 1 depicts atransmission electron microscope (TEM) image of an intercalationcompound having a tungsten disulfide (WS₂) composition with an inorganicfullerene-like geometry. In another example, the intercalation compoundhaving the inorganic fullerene like geometry is composed of molybdenumdisulfide (MoS₂). It is noted that the intercalation compound with theinorganic fullerene like geometry that is depicted in FIG. 1 is notlimited to only tungsten disulfide (WS₂) and molybdenum disulfide(MoS₂). Intercalation compounds having a fullerene-like geometry mayhave any inorganic composition that meets the formula MX₂, where M is ametallic element selected from the group consisting of titanium (Ti),vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co),nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb),molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh),palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta),tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt),gold (Au) and mercury (Hg), and X is a chalcogen element selected fromthe group consisting of Sulfur (S), selenium (Se), tellurium (Te) andoxygen (O). The intercalation compound having an inorganic fullerenelike geometry may have a diameter ranging from 1 nm to 15 μm. In anotherembodiment, the intercalation compound may have a diameter ranging from2 nm to 10 μm. In yet another embodiment, the intercalation compound mayhave a diameter ranging from 5 nm to 5 μm. In some examples, theintercalation compound having an inorganic fullerene like geometry mayhave a diameter ranging from 20 nm to 500 nm. In other examples, theintercalation compound having the inorganic fullerene like geometry mayhave a diameter ranging from 30 nm to 200 nm. The intercalation compoundhaving the inorganic fullerene-like geometry may have a diameter that isany value within the above ranges. It is noted that the above dimensionsare provided for illustrative purposes only, and are not intended tolimit the present disclosure.

As used herein, the term “tube-like geometry” denotes a columnar orcylindrical geometry, in which one axis of the intercalation compound.In some embodiments, an intercalation compound having an inorganictube-like geometry may be a cage geometry that is hollow or solid at itscore and layered at its periphery. In one example, the tube-likegeometry may be a cage geometry that is amorphous at its and layered atits periphery. For example, the intercalation compound having theinorganic tithe-like geometry may be a single layer or double layeredstructure. These structures are also referred to in the art as being“nested layer structures”.

One example of an intercalation compound having an inorganic fullerenegeometry is depicted in FIG. 2. FIG. 2 depicts a transmission electronmicroscope (TEM) image of an intercalation compound having a tungstendisulfide (WS₂) composition with an inorganic tubelike geometry. Inanother example, the intercalation compound having the inorganictube-like geometry is composed of molybdenum disulfide (MoS₂). It isnoted that the intercalation compound with the inorganic tube-likegeometry that is depicted in FIG. 2 is not limited to only tungstendisulfide (WS₂) and molybdenum disulfide (MoS₂). Intercalation compoundshaving a tube-like geometry may have any inorganic composition thatmeets the formula MX₂, where M is a metallic element selected from thegroup consisting of titanium (Ti), vanadium (V), chromium (Cr),manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc(Z), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc),ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd),hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os),iridium (Ir), platinum (Pt), gold (Au) and mercury (Hg), and X is achalcogen element selected from the group consisting of Sulfur (S),selenium (Se), tellurium (Te) and oxygen (O).

The intercalation compound having an inorganic tube-like geometry mayhave a diameter ranging from 1 nm to 300 nm. In another embodiment, theintercalation compound may have an inorganic tube-like geometry with adiameter, i.e., distance perpendicular to the greatest axis of thetube-like geometry, ranging from 5 nm to 150 nm. In yet anotherembodiment, the intercalation compound may have an inorganic tube-likegeometry with a diameter ranging from 10 nm to 100 nm. The intercalationcompound having the inorganic tube-like geometry may have a length,i.e., greatest axis of the tube-like geometry, that ranges from 1 nm to20 cm. In another embodiment, the intercalation compound having theinorganic tube-like geometry may have a length, i.e., greatest axis ofthe tube-like geometry, that ranges from 5 nm to 15 cm. In yet anotherembodiment, the intercalation compound having the inorganic tube-likegeometry may have a length, i.e., greatest axis of the tube-likegeometry, that ranges from 100 nm to 10 cm. The intercalation compoundhaving the inorganic tube-like geometry may have a length or diameterthat is any value within the above ranges. For example, inorganictube-like geometry intercalation compounds may have a length rangingfrom 5 microns to 20 microns. It is noted that the above dimensions areprovided for illustrative purposes only, and are not intended to limitthe present disclosure.

The intercalation compound having the metal chalcogenide composition,e.g., WS₂, and the fullerene-like geometry and/or tubular-like geometrymay be produced via sulfidization of tungsten oxide nanoparticles inreduction atmosphere in fluidized bed reactor. The intercalationcompound my be formed in accordance with at least one of the methodsdisclosed in U.S. Pat. Nos. 6,217,843, 6,710,020, 6,841,142, 7,018,606and 7,641,886, which are each incorporated herein in their entirety. Itis noted that the methods disclosed in the forementioned patents areonly some examples of methods that are suitable for forming theintercalation compound. Any method may be employed for forming theabove-described intercalation compound, so long as the compound formedhas a fullerene-like or tube-like geometry.

The intercalation compound of the inorganic fullerene-like and/ortube-like geometry is formula MX₂. The metallic elements that aresuitable for M in the formula MX₂, and the chalcogen elements that aresuitable for X in the formula MX₂ are provided above.

The surface of the inorganic fullerene-like and/or tube-like having themolecular formula MX₂ is functionalized or modified in order to obtaintheir homogeneous dispersion in the fluid medium of the lubricant,prevent particles agglomeration and settling. A “dispersion” is a systemof two phases, in which discrete particles, i.e., primary particles,such as the inorganic fullerene-like and/or tube-like having themolecular formula MX₂, provide a first phase that are distributed in theother second phase, in which the second phase is a substantiallycontinuous phase (dispersion medium) differing from the dispersed phasein composition. Dispersions are homogeneous when the ratio of solute,i.e., primary particles, such as the inorganic fullerene-like and/ortube-like having the molecular formula MX₂, to solvent, i.e., fluidmedium, remains the same throughout the solution even if homogenizedwith multiple sources, and stable because, the solute will not settleout. This type of mixture, which is provided by the methods andcompositions disclosed herein, is very stable, i.e., its particles donot settle, or separate. As used herein, “agglomeration” means anassociation of primary particles, which can range from relatively weak(based upon, for example, charge or polarity) to relatively strong(based upon, for example, chemical bonding). When the primary particles,i.e., inorganic fullerene-like and/or tube-like having the molecularformula MX₂, agglomerate they can fall, i.e., settle, from suspension.The methods and compositions that are provided herein providedispersions that do not agglomerate or settle for a period of time thatmay be as great as 5 years, e.g., as great as 3 years. The dispersionsare stabilized from agglomeration or settling by the functionalizationagents that is described below, and the particle size that is providedby mechanical downgrading, such as particle size reductions provided bymilling and/or high pressure homogenization and/or high shear mixingand/or ultrasonic mixing and/or a combination thereof.

The surface of the inorganic fullerene-like and/or tube-like particleshaving the molecular formula MX₂ may be functionalized or modified byforming an adsorption-solvate protective layer on the particle surfaces,i.e., surface of the inorganic fullerene-like and/or tube-like particleshaving the molecular formula MX₂, and preventing the close approach andcoagulation of particles under the action of short-range forces ofmolecular attraction. The close approach of particles may be impeded bythe disjoining pressure of the liquid dispersion medium, which issolvated by molecules or ions of the stabilizer in the adsorption layer,by electrostatic repulsion of like-charged ions adsorbed on the particlesurfaces, or by enhanced structural viscosity of the surface protectivelayer, which can also be referred to as being a structural-mechanicalbarrier.

Surface functionalization for the surface of the inorganicfullerene-like and/or tube-like particles having the molecular formulaMX₂ may by provided by functionalizing agents that include silanes,thiols, ionic, anionic, cationic, nonionic surfactants, amine baseddispersant and surfactants, succinimide groups, fatty acids, acrylicpolymers, copolymers, polymers, monomers and combinations thereof.

In some embodiments, the functionalizing agents can be described ascomprising a headgroup (a part that interacts primarily with the surfaceof the inorganic fullerene-like and/or tube-like particles having themolecular formula MX₂) and a tailgroup (a part that interacts with thesolvent, i.e., fluid medium). Useful headgroups include those thatcomprise alkoxy, hydroxyl, halo, thiol, silanol, amino, ammonium,phosphate, phosphonate, phosphonic acid, phosphinate, phosphinic acid,phosphine oxide, sulfate, sulfonate, sulfonic acid, sulfinate,carboxylate, carboxylic acid, carbonate, boronate, stannate, hydroxamicacid, and/or like moieties. Multiple headgroups can extend from the sametailgroup, as in the case of 2-dodecylsuccinic acid and (1-aminooctyl)phosphonic acid. Useful hydrophobic and/or hydrophilic tailgroupsinclude those that comprise single or multiple alkyl, aryl, cycloalkyl,cycloalkenyl, haloalkyl, oligo-ethylene glycol, oligo-ethyleneimine,dialkyl ether, dialkyl thioether, aminoalkyl, and/or like moieties.Multiple tailgroups can extend from the same headgroup, as in the caseof trioctylphosphine oxide.

Examples of silanes that are suitable for use as functionalizing agentswith the inorganic fullerene-like and/or tube-like particles having themolecular formula MX₂ and the fluid medium of the present disclosureinclude organosilanes including, e.g., alkylchlorosilanes,alkoxysilanes, e.g., methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, propyltrimethoxysilane, ipropyltriethoxysilane,butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane,octyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane,n-octyltriethoxysilane, phenyltriethoxysilane, polytriethoxysilane,vinyltrimethoxysilane, vinyldimethylethoxysilane,vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane,vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane,vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri(t-butoxy)silane,vinyltris(isobutoxy)silane, vinyltris(isopropenoxy)silane, andvinyltris(2-methoxyethoxy)silane; trialkoxyarylsilanes;isooctyltrimethoxysilane; N-(3-triethoxysilylpropy-1)methoxyethoxyethoxyethyl carbamate; N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethylcarbamate; silane functional (meth)acrylates including, e.g.,3-(methacryloyloxy)propyltrimethoxysilane,3-acryloyloxypropyltrimethoxysilane,3-(methacryloyloxy)propyltriethoxysilane,3-(methacryloyloxy)propylmethyldimethoxysilane,3-(acryloyloxypropyl)methyldimethoxysilane,3-(methacryloyloxy)propyldimethylethoxysilane,3-(methacryloyloxy)methyltriethoxysilane,3-(methacryloyloxy)methyltrimethoxysilane,3-(methacryloyloxy)propyldimethylethoxysilane,3-methacryloyloxy)propenyltrimethoxysilane, and3-(methacryloyloxy)propyltrimethoxysilane; polydialkylsiloxanesincluding, e.g., polydimethylsiloxane, arylsilanes including, e.g.,substituted and unsubstituted arylsilanes, alkylsilanes including, e.g.,substituted and unsubstituted alkyl silanes including, e.g., methoxy andhydroxy substituted alkyl silanes, and combinations thereof.

Examples of amines that are suitable for use as functionalizing agentswith the inorganic fullerene-like and/or tube-like particles having themolecular formula MX₂ and the fluid medium of the present disclosureinclude alkylamines including, e.g., octylamine, oleylamine, decylamine,dodecylamine octadecylamine, monopolyethylene glycol amines, andcombinations thereof.

Useful organic acid functionalizing agents include, e.g., oxyacids ofcarbon (e.g., carboxylic acid), sulfur and phosphorus, and combinationsthereof.

Representative examples of polar functionalizing agents havingcarboxylic acid functionality include CH₃O(CH₂CH₂O)₂C—H₂COOH (hereafterMEEAA) and 2-(2-methoxyethoxy)acetic acid having the chemical structureCH₃OCH₂CH₂OCH₂COOH hereafter MEAA) and mono (polyethylene glycol)succinate in either acid or salt forms.

Representative examples of non-polar functionalizing agents havingcarboxylic acid functionality include octanoic acid, dodecanoic acid andoleic acid.

Examples of suitable phosphorus containing acids that are suitable asfunctionalizing agents include phosphonic acids including, e.g.,octylphosphonic acid, laurylphosphonic acid, decylphosphonic acid,dodecylphosphonic acid, octadecylphosphonic acid, and monopolyethyleneglycol phosphonate in either acid or salt forms.

Examples of other useful functionalizing agents include acrylic acid,methacrylic acid, beta-carboxyethyl acrylate,mono-2-(methacryloyloxyethyl)succinate, and combinations thereof. Auseful surface modifying agent ismono(methacryloyloxypolyethyleneglycol-)succinate.

Examples of suitable alcohols for functionalizing agents include, e.g.,aliphatic alcohols including, octadecyl, dodecyl, lauryl and furfurylalcohol, alicyclic alcohols including, e.g., cyclohexanol, and aromaticalcohols including, e.g., phenol and benzyl alcohol, and combinationsthereof.

In some embodiments, the functionalizing agents may be introduced to theinorganic fullerene-like and/or tube-like particles having the molecularformula MX₂ during their formation prior to having the opportunity toagglomerate or destabilize from solution. In other embodiments,agglomerates of the inorganic fullerene-like and/or tube-like particleshaving the molecular formula MX₂ are first mechanically broken down intotheir primary size, i.e., the size of the primary particles prior toagglomeration. The mechanical reduction of the agglomerates of theinorganic fullerene-like and/or tube-like particles having the molecularformula MX₂ to their primary size may be referred to as milling.

In some embodiments inorganic fullerene nanoparticles can be mixed withother solid particles, which may be from 1 nm to 10 microns in size,such as carbon fullerenes, carbon nanotubes, graphite, 2H—MoS₂, 2H—WS₂,boron, Zn, Cu, silver, graphite, MgOH, carbon diamond or combinations ofthereof.

In some embodiments, the milling process may begin with agglomerateshaving a particle size ranging from 5 microns to 20 microns. Theparticles size of the agglomerates may be reduced using a high-shearmixer, two or three roll mixers, homogenizers, bead mills, ultrasonicpulverizer and a combination thereof. A high-shear mixer disperses, ortransports, one phase or ingredient (liquid, solid, gas) into a maincontinuous phase (liquid), with which it would normally be immiscible. Arotor or impellor, together with a stationary component known as astator, or an array of rotors and stators, is used either in a tankcontaining the solution to be mixed, or in a pipe through which thesolution passes, to create shear. In some embodiments, the high shearmixer may be a batch high-shear mixers, an inline powder induction, ahigh-shear granulator, an ultra-high-shear inline mixers and acombinations thereof.

Other means for reducing the particle size of the agglomerates to theprimary particle size of the inorganic fullerene-like and/or tube-likeparticles having the molecular formula MX₂ include an attritor,agitator, ball mill, bead mill, basket mill, colloid mill, high speeddisperser, edge runner, jar mill, low speed paddle mixer, variable speedmixer, paste mixer, ribbon blender, pug mixer, nauta mixer, sand/perlmill, triple roll mill, two roll mill, planetary mixer, slow speedmixer, high speed mixer, twin shaft mixer, multi shaft mixer, sigmakneader, rotor-stator mixer, homogenizer/emulsifier, high shear mixer,conical blender, V-blender, double cone blender, suspended mixer andcombinations thereof. The particle size of the agglomerates may also bereduced using a sonicator. The mixing may be performed at roomtemperature or at an elevated temperature.

In some embodiments, the fluid medium for the lubricant is mixed withthe inorganic fullerene-like and/or tube-like particles having themolecular formula MX₂ during the milling step in which the agglomeratesof the inorganic fullerene-like and/or tube-like particles having themolecular formula MX₂ are mechanically broken down into their primarysize. The inorganic fullerene-like and/or tube-like particles having themolecular formula MX₂ may be mixed with the fluid medium in an amountranging from 0.1% to 60% by volume. In another embodiment, the inorganicfullerene-like and/or tube-like particles having the molecular formulaMX₂ may be mixed with the fluid medium in an amount ranging from 0.5% to40% by volume. In yet another embodiment, the inorganic fullerene-likeand/or tube-like particles having the molecular formula MX₂ may be mixedwith the fluid medium in an amount ranging from 0.5% to 20% by volume.

In some embodiments, the agglomerates of the inorganic fullerene-likeand/or tube-like particles having the molecular formula MX₂ is reducedduring the milling step to a diameter ranging from 1 nm to 15 μm forfullerene like geometries. In another embodiment, the agglomerates ofthe inorganic fullerene-like and/or tube-like particles having themolecular formula MX₂ is reduced during the milling step to a diameterranging from 2 nm to 10 μm for fullerene like geometries. In yet anotherembodiment, the agglomerates of the inorganic fullerene-like and/ortube-like particles having the molecular formula MX₂ is reduced duringthe milling step to a diameter ranging from 5 nm to 5 μm for fullerenelike geometries. Following milling, the inorganic fullerene-like and/ortube-like particles having the inorganic fullerene like geometry mayhave a diameter that is any value within the above ranges. It is notedthat the above dimensions are provided for illustrative purposes only,and are not intended to limit the present disclosure.

In some embodiments, the agglomerates of the inorganic fullerene-likeand/or tube like particles having the molecular formula MX₂ is reducedduring the milling step to a diameter ranging from 1 nm to 150 nm, and alength that ranges from 1 nm to 20 cm, for tube like geometries. Inanother embodiment, the agglomerates of the inorganic fullerene-likeand/or tube-like particles having the molecular formula MX₂ is reducedduring the milling step to a diameter ranging from 5 nm to 125 nm, and alength that ranges from 5 nm to 15 cm, for tube like geometries. In yetanother embodiment, the agglomerates of the inorganic fullerene-likeand/or tube-like particles having the molecular formula MX₂ is reducedduring the milling step to a diameter ranging from 10 nm to 100 nm, anda length that ranges from 100 nm to 10 cm, for tube-like geometries.Following milling, the inorganic fullerene-like and/or tube-likeparticles having the inorganic tube-like geometry may have a diameterand length that is any value within the above ranges. It is noted thatthe above dimensions are provided for illustrative purposes only, andare not intended to limit the present disclosure.

In some embodiments, once the agglomerates of the inorganicfullerene-like and/or tubelike particles having the molecular formulaMX₂ are broken down into their primary size, the functionalizing agentmay be added to the mixture of the fluid medium and the inorganicfullerene-like and/or tube-like particles having the molecular formulaMX₂.

A functionalizing agent of amine may be added to the mixture in anamount ranging from 0.1 wt % to 50 wt. % of the inorganic fullerene-likeand/or tube-like particles. For example, when functionalizing agent isan amine, such as oleylamine, the minimum functionalizing agent would be0.1 g for 1 gram of inorganic fullerene-like and/or tube-like particleshaving the molecular formula MX₂, e.g. 1 gram of fullerene-like tungstendisulfide (WS₂), in 100 grams of the fluid medium, e.g., an olefin basedoil. For example for 100 grams of isomerized alpha olefin fluid(drilling fluid) 1 wt % i.e. 1 gram of WS₂ fullerene-like particles and0.1 gram of oleilamine are added). In another example, whenfunctionalizing agent is an amine, such as oleylamine, the maximumfunctionalizing agent would be 20 grams for 1 gram of inorganicfullerene-like and/or tube-like particles having the molecular formulaMX₂, e.g. 1 gram of fullerene-like tungsten disulfide (WS₂) ormolybdenum disulfide (MoS₂), in 100 grams of the fluid medium, e.g., anolefin based oil.

A functionalizing agent of silane may be added to the mixture in anamount ranging from 0.1 wt % to 50 wt. % of the inorganic fullerene-likeand/or tube-like particles. For example, when functionalizing agent is asilane, e.g., octadecyltrichlorosilane (OTS), the minimumfunctionalizing agent would be 0.1 g for 1 gram of inorganicfullerene-like and/or tube-like particles having the molecular formulaMX₂, e.g., 1 gram of fullerene-like tungsten disulfide (WS₂), in 100grams of the fluid medium, e.g., an olefin based oil. In anotherexample, when functionalizing agent is an silane, e.g.,octadecyltrichlorosilane (OTS), the maximum functionalizing agent wouldbe 50 grams for 1 gram of inorganic fullerene-like and/or tube-likeparticles having the molecular formula MX₂, e.g. 1 gram offullerene-like tungsten disulfide (WS₂), in 100 grams of the fluidmedium, e.g., an olefin based oil.

The functionalizing agent applied to the mixture of the fluid medium andthe inorganic fullerene-like and/or tube-like particles having themolecular formula MX₂ provide dispersions that do not agglomerate orsettle for a period of time that may range from 3 hours to 5 years. Inanother embodiment, the functionalizing agent applied to the mixture ofthe fluid medium and the inorganic fullerene-like and/or tube-likeparticles having the molecular formula MX₂ provide dispersions that donot agglomerate or settle for a period of time that may range from 5hours to 3 years. In yet another embodiment, the functionalizing agentapplied to the mixture of the fluid medium and the inorganicfullerene-like and/or tube-like particles having the molecular formulaMX₂ provide dispersions that do not agglomerate or settle for a periodof time that may range from 24 hours to 1 year.

In one embodiment, the lubricant further includes an additive forantiwear performance, extreme pressure performance, anticorrosionperformance, rust inhibiting performance, antifoam, viscosity modifying,friction modifying additives. The extreme pressure and antiwearadditives may be selected from at least one of organophosphorus,organophosphorus sulfur, organosulphur, chlorine,sulfur-phosphorus-boron compounds and combinations thereof.

FIG. 3 depicts the application of the lubricant including the fluidmedium containing the inorganic fullerene-like and/or tube-likeparticles having the molecular formula MX₂ and the functionalizing agentto a surface to be lubricated. FIG. 3 depicts how the sphere geometry ofthe inorganic fullerene-like particles 10 having the molecular formulaMX₂ provide roller effect when simultaneously in contract with opposingsurfaces 15, 20 that are being lubricated. More specifically, therolling action of the sphere geometry of the inorganic fullerene-likeparticles 10 provides a low friction sliding motion between the opposingsurfaces 15, 20 being lubricated. The sphere geometry of the inorganicfullerene-like particles 10 acts as an anti-friction agent enhancing theeffectiveness of the fluid lubricant. The column shape of the tube-likeparticles having the molecular formula MX₂ provide a roller effectsimilar to the performance that is provided by the sphere geometry ofthe inorganic fullerene-like particles 10.

FIGS. 4 and 5 further depict a surface reconditioning effect that isprovided by the lubricant including the fluid medium containing theinorganic fullerene-like and/or tube-like particles 10 having themolecular formula MX₂ and the functionalizing agent. More specifically,the inorganic fullerene-like and/or tube-like particles 10 having themolecular formula MX₂ are layered structures, in which when the exteriorlayers contact the surface being lubricated, the exterior layer 11 peels(also referred to as exfoliates) from the inorganic fullerene-likeand/or tube-like particles and adheres to the surface 16 beinglubricated, as depicted in FIG. 5. An inorganic fullerene-like and/ortube-like particle of tungsten disulfide (WS₂) may have alternatinglayers of tungsten (W) and sulfur (S). An inorganic fullerene-likeand/or tube-like particle of molybdenum disulfide (MoS₂) may havealternating layers of molybdenum (Mo) and sulfur (S). One molybdenum(Mo) atom is sandwiched between two hexagonally packed sulfur atoms. Thebonding between Mo and two S is covalent, however the bonding betweeneach MoS₂ sandwich is week (Vander Waals). In this manner, the inorganicfullerene-like and/or tube-like particles having the molecular formulaMX₂, such as molybdenum disulfide (MoS₂) and tungsten disulfide (WS₂),can deposit a metal-chalcogen (metal-sulfide for example) layer, such asmolybdenum (MoS₂) or tungsten (WS₂), on the eroded surface beinglubricated. Therefore, the inorganic fullerene-like and/or tube-likeparticle can recondition eroded surfaces, i.e., smooth rough and damagedsurfaces, and lubricate to protect from additional wear. In someembodiments, the hollow feature of the inorganic fullerene-like and/ortube-like particle provides enhanced impact resistance.

In some embodiments, the lubricant may further include a carboncontaining nanomaterial, such as carbon nanotubes, e.g., single wallcarbon nanotubes (CNT) or multi-wall carbon nanotubes (SWNT), orgraphitic materials, such as carbon black (CB), graphitic fibers,graphite platelets and diamond like carbon (DLC). In one embodiment, thecarbon containing nonmaterial is provided by carbon nanotubes that mayhave a high purity on the order of about 95% to about 99% carbon. In aneven further embodiment, the carbon nanotubes have a high purity on theorder of about 99% or greater. In one embodiment, the carbon nanotubesmay be provided by laser vaporization. In one embodiment, the singlewall carbon nanotubes are formed using laser vaporization in combinationwith a catalyst, such as a metal catalyst. In one embodiment, thecatalyst is supported on a substrate, such as a graphite substrate, orthe catalyst may be floating metal catalyst particles. In oneembodiment, the metal catalyst may be composed of Fe, Ni, Co, Rh, Y oralloys and combinations thereof.

The diameter of a single wall carbon nanotube may range from about 1nanometer to about 50 nanometers. In another embodiment, the diameter ofa single wall carbon nanotube may range from about 1.2 nanometers toabout 1.6 nanometers. In one embodiment, the nanotubes used inaccordance with the present invention have an aspect ratio of length todiameter on the order of approximately 200:1.

The carbon nanotubes comprise a majority of carbon typically being ofhigh purity. In other examples, the carbon nanotubes include a carboncontent ranging from being greater than 50%, wherein a purificationprocess is utilized to provide carbon nanotubes having of high purity,such as greater than 90% carbon. In one embodiment, the carbon nanotubesmay be purified by a process that includes an acid treatment followed byan oxidation. In one embodiment, the acid treatment may includetreatment and oxidation steps are provided by a dilute HNO₃ reflux/airoxidation procedure.

Other methods of forming the carbon nanotubes may also be employed, suchas chemical vapor deposition (CVD). In another embodiment, the carbonnanotubes may be multi-walled, Carbon black (also known as acetyleneblack, channel black, furnace black, lamp black or thermal black) isalso suitable for providing the at least one carbon containingnanomaterial that is present in the lubricant. Carbon black is amaterial produced by the incomplete combustion of heavy petroleumproducts such as FCC tar, coal tar, ethylene cracking tar, and a smallamount from vegetable oil.

In some embodiments, the carbon containing nanomaterial may be presentin the lubricant in an amount ranging from 0.1 wt % to 50 wt. %. Inanother embodiment, the carbon containing nanomaterial may be present inthe lubricant in an amount ranging from 0.1 wt % to 40 wt. %. In yetanother embodiment, the carbon containing nanomaterial in the lubricantin an amount ranging from 0.1 wt % to 25 wt. %.

In some applications, the above described lubricant may be suitable forengine oil treatments for automotive, transportation, and generatorapplications. For example, the engine oil treatments may be suitable forgasoline and diesel engines used in cars, trucks, industrial engines,boats and motorcycles. Other automotive applications for the abovedescribed lubricant include gears, transmissions, e.g., manual andautomatic transmissions, rear and front differentials, transfer cases,such as those used in 4×4 vehicles and trucks, and final driveapparatus, such as those used in tractors and earth moving equipment.Industrial applications include gears, chains, conveyors, and slidingcomponents.

In another application, the methods and compositions can provide adrilling fluid for subterranean drilling. FIG. 6 is a pictorial view ofa drilling operation using the drilling fluid (flow identified byreference number 40) including the intercalation compound of a metalchalcogenide having molecular formula MX₂, which has a fullerene-likeand/or tube like geometry. In one embodiment, the subterranean drillingmethod may include providing a drilling member 50, and applying thedrilling member 50 to a terrane an surface to form a subterraneanwellbore 60. The drilling member 50 includes at least a drill string anda drill component.

The subterranean drilling method may further include lubricating atleast one of the subterranean wellbore 19 and the drilling member 50with a fluid including at least one intercalation compound of a metalchalcogenide having molecular formula MX₂, where M is a metallic elementselected from the group consisting of titanium (Ti), vanadium (V),chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni),copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo),technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver(Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium(Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg)and combinations thereof, and X is a chalcogen element selected from thegroup consisting of sulfur (S), selenium (Se), tellurium (Te), oxygen(O) and combinations thereof. The intercalation compound has afullerene-like structure or tubular-like structure. The intercalationcompound is present in the drilling fluid 40 in an amount of greaterthan 0.1 wt % by weight. In some embodiments, the drilling fluid 40 mayfurther includes a functionalizing agent. The functionalizing agentprovides that the intercalation compound is kept in suspension withinthe drilling fluid 40.

Drilling fluid, also referred to as drilling mud, is used to aid thedrilling of boreholes, also referred to as wellbores 50, into the earth.Often used while drilling oil and natural gas wells and on explorationdrilling rigs, drilling fluids are also used for much simpler boreholes,such as water wells. One of the most critical roles of drilling mud isas a lubricant. Drilling generates tremendous friction, which can damagethe drill or the formation being drilled. Drilling mud cuts down on thefriction, lowering the heat of drilling and reducing the risk offriction-related complications. The mud also acts as a carrier for thematerials being drilled, with material becoming suspended in the mud andthen being carried up the drill to the surface. Using drilling mudprotects the stability of a borehole by controlling variables such asfriction and pressure. In some embodiments, the function of drillingfluids further include providing hydrostatic pressure to preventformation fluids from entering into the well bore, keeping the drill bitcool 70 and clean during drilling, carrying out drill cuttings, andsuspending the drill cuttings while drilling is paused and when thedrilling assembly is brought in and out of the hole.

In some embodiments, the fluid medium for the drilling fluid used inaccordance with the methods and structures disclosed herein may beselected from the group consisting of water, air and water, air andfoaming agent, a water based mud, an oil based mud, a synthetic basedfluid, and a combination thereof. A most basic water-based mud systembegins with water, then clays and other chemicals are incorporated intothe water to create a homogenous blend. The clay (called “shale” in itsrock form) is usually a combination of native clays that are suspendedin the fluid white drilling, or specific types of clay that areprocessed and sold as additives for the water-based mud system. Oneexample of an additive used in water-based mud systems is bentonite.Other additives, such as calcium chloride, calcium bromide, zincbromide, potassium formate, calcium carbonate, ground cellulose,bentonite, natural & synthetic polymer, asphalt and gilsonite, are addedto a water based mud system to achieve various effects, including:viscosity control, shale stability, enhance drilling rate ofpenetration, cooling and lubricating of equipment.

Oil-based mud can be a mud where the base fluid is a petroleum productsuch as diesel fuel. Oil-based muds contain oil as the continuous phaseand water as a contaminant, and not an element in the design of the mud.They typically contain less than 5% (by volume) water. Oil-based mudsare usually a mixture of diesel fuel and asphalt, however can be basedon produced crude oil and mud. Oil-based muds are used for many reasons,some being increased lubricity, enhanced shale inhibition, and greatercleaning abilities with less viscosity. Oil-based muds also withstandgreater heat without breaking down. Additives for oil based muds includeemulsifying agents (alkaline soaps and fatty acids), vetting agents(dodecylbenzene sulfonate), water, barite or barium sulfate, (weightingagent), asbestos (employed as viscosification agent) and/or,aminetreated clays (also as viscosification agent). Synthetic-basedfluid (Otherwise known as Low Toxicity Oil Based Mud or LTOBM) is a mudwhere the base fluid is a synthetic oil.

Some other additives that may be employed in drilling fluids includecalcium carbonate, crushed or ground marble, limestone, dolomite(calcium magnesium carbonate), zinc carbonate, barium carbonate, lithiumcarbonate, iron carbonate, other metal carbonates, hematite, ilmenite,magnesium oxide, manganese tetroxide, zinc oxide, magnesium oxychloride,colemanite, analcite, apatite, bauxite, brucite, gibsite, hydrotalcite,other metal oxides, metal hydroxides, magnesium oxysulfate, other metalsulfates, metal tungstates, metal fluorides, lithium phosphate, othermetal phosphates, magnesium sulfite, lead sulfide, metal peroxides,magnesium potassium phosphate hexahydrate, magnesium hydrogen phosphatetrihydrate, magnesium ammonium phosphate hexahydrate, metalfluorosilicates, sodium chloride, other water-soluble salts, crushed orground nut shells, crushed or ground seeds, crushed or ground fruitpits, materials obtained from barks of trees, calcined petroleum coke,asphalts, barite particles, clay particles, micaparticles, talcparticles, silica particles, sands, feldspar, bauxite particles, ceramicparticles, cement particles, melamine, solid or hollow micro spheres,graphitic materials, other forms of carbon, celluloses, starches,polysaccharides, acrylic polymers, natural rubbers, synthetic rubbers,styrene-diene diblock and triblock copolymers, other natural Orsynthetic polymers, expanded polystyrene beads, other foam beads, carbonfibers, glass fibers, polymer fibers, other fibers, water, dispersants,thinners, crystalline additives of low molecular weight (such as1-Sendo-Bomeol, camphor, iodine, beta carotene, lycophene, cholesterol,lanosterol, or agnosterop, and combinations thereof.

It is noted that the above described fluid mediums and the inorganicfullerene-like and/or tube-like particles having the molecular formulaMX₂ for the lubricants described with reference to FIGS. 1-5, may besuitable for use with the drilling fluid that is described withreference to FIG. 6. Further, the inorganic fullerene-like and/ortube-like particles having the molecular formula MX₂ may be stabilizedwithin the drilling fluid using the functionalizing agents and methodsthat are also described above with reference to FIGS. 1-5.

The lubricants and drilling fluids disclosed herein provide an increasein friction reduction of up to two times, and more, when compared toconventional materials, and a wear reduction of up to three times, andmore. The lubricants and drilling fluids disclosed herein also provide asurface reconditioning effect. Applications for the drilling fluidsdisclosed herein may include application to drill string, bit and othermechanical parts used in subterranean drilling. Other applications forthe lubricants disclosed herein can include ski waxes, anti-stickcoatings and antistick scratches.

The following examples are provided for illustrative purposes and arenot intended to limit the present disclosure.

EXAMPLES

Friction Reduction

Pin on disc tests (stainless steel (SS) ball or a stainless steel (SS)substrate) were performed using test samples of drilling fluid of anisomerized alpha olefin (hydrocarbon fluid with isomerized moleculesrearranged) with additives of 2% tungsten disulfide (WS₂) fullerene-likegeometry particles and a functionalization agent of ε-caprolactammonomer, and a comparative sample of drilling fluid of an isomerizedalpha olefin (hydrocarbon fluid with isomerized molecules rearranged)without additives. The test included a 1N load, a 0.4 cm/s speed and atest duration of 30 minutes. The data was plotted in FIG. 7, in whichthe tests samples of drilling fluid of an isomerized alpha olefin(hydrocarbon fluid with isomerized molecules rearranged) with additivesof 2% tungsten disulfide (WS₂) fullerene-like geometry particles and afunctionalization agent of E-caprolactam monomer are identified in FIG.7 as “base fluid WS₂+E 2%-test 1” and “base fluid WS₂+E 2%-test 2”. Thedata from testing of the comparative sample is identified in FIG. 7 as“base fluid”. The data included in FIG. 7 illustrated a 36% decrease infriction for the test samples of isomerized alpha olefin with additivesof 2% tungsten disulfide (WS₂) fullerene-like geometry particles and afunctionalization agent of ε-caprolactam monomer when compared to thecomparative sample that did not include the tungsten disulfide (WS₂)fullerene-like geometry particles. There was also no measurable frictionincrease measured for the test samples of isomerized alpha olefin withadditives of 2% tungsten disulfide (WS₂) fullerene-like geometryparticles over a period of 650 cycles.

Wear Reduction

FIG. 8 depicts profilometry curves measured for the ball from the pin ondisc test that provided the data in FIG. 7. The profilometry curveplotted in FIG. 8 for the test sample is identified as “base fluid WS₂+E2%-test 1”. The profilometry curve plotted in FIG. 8 for the comparativesample is identified as “base fluid”. The profilometry curves measuredfrom the ball of the pin on disc test that included the drilling fluidof isomerized alpha olefin (hydrocarbon fluid with isomerized moleculesrearranged) with additives of 2% tungsten disulfide (WS₂) fullerene-likegeometry particles and a functionalization agent of ε-caprolactammonomer indicated no wear. FIGS. 9B and 9C are optical microscope imagesof the ball from the pin on disc test including the drilling fluidisomerized alpha olefin (hydrocarbon fluid with isomerized moleculesrearranged) with additives of 2% tungsten disulfide (WS₂) fullerene-likegeometry particles and a functionalization agent of E-caprolactammonomer. There is not visible wear depicted in FIGS. 9B and 9C. Theprofilometry curve for the ball of the comparative, example ofisomerized alpha olefin without tungsten disulfide (WS₂) fullerene-likegeometry particles illustrated ball volume loss. Specifically, a scarhaving a depth of 0.5 μm was measured. The scar on the ball from thecomparative example test is clearly depicted in the optical microscopeimage depicted in FIG. 9A.

Reduction of Engine Wear

FIG. 10 is a plot of engine wear (measured by presence of iron (Fe) inoil (ppm) as a function of engine run time for a sample of 30 SAE oilincluding at least one intercalation compound of a metal chalcogenidehaving molecular formula MX₂ in comparison with a comparative sample of30 SAE oil without the intercalation compound. In this example, theintercalation compound was fullerene like tungsten disulfide (WS₂)having a diameter ranging from 30 nm to 200 nm, and present in 30 SAEoil in an amount ranging from 0.1 wt % to 7 wt %. The plot identified byreference number 100 is the engine wear as a function of engine run timemeasured by the presence of iron (Fe) (worn from internal enginecomponents) in SAE 30 oil lubricating the internal engine componentsduring engine run time, wherein the oil lubricating the engine duringthe engine run time contained fullerene like tungsten disulfide (WS₂)intercalation compounds, in accordance with lubricants disclosed herein.The plot identified by reference number 200 is a comparative example,which was run in an identical engine using identical SAE oil with theexception that the oil did not include fullerene like tungsten disulfide(WS₂) intercalation compounds. The dashed line identified by referencenumber 150 illustrates the oil change level of iron (Fe) being measuredin the oil. As indicated by plot in FIG. 10, when the engine run timeapproaches approximately 90 hours the iron content within thecomparative example of oil (which does not contain fullerene liketungsten disulfide (WS₂) intercalation compounds) reaches the oil changelevel, whereas the iron (Fe) content in the oil treated with thefullerene like tungsten disulfide (WS₂) intercalation compounds does notreach the oil change level for up to approximately 180 hours.

While the claimed methods and structures has been particularly shown anddescribed with respect to preferred embodiments thereof, it will beunderstood by those skilled in the art that the foregoing and otherchanges in form and details may be made therein without departing fromthe spirit and scope of the presently claimed methods and structures.

What is claimed is:
 1. A lubricant comprising: a fluid medium; at leastone intercalation compound of a metal chalcogenide having molecularformula MX₂, where M is a metallic element selected from the groupconsisting of molybdenum (Mo), tungsten (W) and combinations thereof,and X is a chalcogen element of sulfur (S), wherein the intercalationcompound has a fullerene-like structure having a caged geometry that issolid at its core and layered at its periphery and the intercalationcompound is present in the lubricant in an amount of greater than 0.1 wt% by weight, the periphery of the intercalation compound being anexfoliating layer that provides an intercalation material on frictionsurfaces that that at least one intercalation compound contacts; and afunctionalizing agent that interacts with the at least one intercalationcompound of a metal chalcogenide having molecular formula MX₂ to form asuccinimide group surface functionalization on the at least oneintercalation compound to provide a dispersion of the intercalationcompound having the fullerene-like structure with the caged geometrythat does not settle for a period of time ranging from 3 years to 5years at room temperature.
 2. The lubricant of claim 1, wherein thefluid medium comprises Group I, II, III, IV, and V lubricants, syntheticoils, mineral oils, water based and oil based drilling fluids andbio-lubricants or combinations thereof.
 3. The lubricant of claim 2,wherein the synthetic oils comprise polyalpha-olefins, olefins,isomerized olefins, synthetic esters, phosphate esters, silicate esters,polyalkylene glycols or combinations thereof.
 4. The lubricant of claim2, wherein the bio-lubricants comprise lanolin, whale oil, canola oil,castor oil, palm oil, sunflower seed oil, rapeseed oil, tall oil orcombinations thereof.
 5. The lubricant of claim 1, wherein theintercalation compound of the metal chalcogenide is a particle having afullerene-like geometry and a diameter ranging from 5 nm to 5 μm.
 6. Adrilling fluid comprising: a drilling fluid medium selected from thegroup consisting of water, air and water, air and foaming agent, a waterbased mud, an oil based mud, a synthetic based fluid, and a combinationthereof; at least one intercalation compound of a metal chalcogenidehaving molecular formula MX₂, where M is a metallic element selectedfrom the group consisting of titanium (Ti), vanadium (V), chromium (Cr),manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc(Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc),ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd),hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os),iridium (1 r), platinum (Pt), gold (Au), mercury (Hg) and a combinationthereof, and X is a chalcogen element selected from the group consistingof sulfur (S), selenium (Se), tellurium (Te), oxygen (O) and acombination thereof, wherein the intercalation compound has afullerene-like structure having a caged geometry that is solid at itscore and layered at its periphery, the periphery of the intercalationcompound being an exfoliating layer that provides an intercalationmaterial on friction surfaces that that at least one intercalationcompound contacts, and the intercalation compound is present in thedrilling fluid in an amount of greater than 0.1 wt % by weight; and afunctionalizing agent that interacts with the at least one intercalationcompound of a metal chalcogenide having molecular formula MX₂ to form asuccinimide group surface functionalization on the at least oneintercalation compound to provide a dispersion of the intercalationcompound having the fullerene-like structure with the caged geometrythat does not settle for a period of time ranging from 3 years to 5years at room temperature.
 7. The drilling fluid of claim 6, wherein thefunctionalizing agent is present in an amount ranging from 0.1 wt. % to50 wt. %.
 8. The drilling fluid of claim 6, wherein the intercalationcompound of the metal chalcogenide is a particle having a fullerene-likegeometry and a diameter ranging from 5 nm to 5 μm.
 9. The lubricant ofclaim 1, wherein the functionalizing agent is present in an amountranging from 0.1 wt. % to 50 wt. %.
 10. A lubricant comprising: a fluidmedium of synthetic oils having a composition selected from the groupconsisting of polyalpha-olefins, olefins, isomerized olefins, syntheticesters, phosphate esters, silicate esters, polyalkylene glycols andcombinations thereof; at least one intercalation compound of a metalchalcogenide having a composition selected from the group consisting oftungsten disulfide (WS₂), molybdenum disulfide (MoS₂) and a combinationthereof, wherein the intercalation compound has a fullerene-likestructure having a caged geometry that is solid at its core and layeredat its periphery and the intercalation compound is present in thelubricant in an amount of greater than 0.1 wt % by weight, the peripheryof the intercalation compound being an exfoliating layer that providesan intercalation material on friction surfaces that that at least oneintercalation compound contacts; and a functionalizing agent thatinteracts with the at least one intercalation compound of the metalchalcogenide selected from the group consisting of tungsten disulfide(WS₂), molybdenum disulfide (MoS₂) and a combination thereof to form asuccinimide group surface functionalization on the at least oneintercalation compound to stabilize a dispersion of the at least oneintercalation compound in the fluid medium by resisting agglomeration ofthe intercalation compound having the fullerene-like structure with thecaged geometry.